U.S. patent number 8,853,475 [Application Number 12/969,335] was granted by the patent office on 2014-10-07 for process for producing a renewable hydrocarbon fuel.
This patent grant is currently assigned to UOP LLC. The grantee listed for this patent is Tom N. Kalnes. Invention is credited to Tom N. Kalnes.
United States Patent |
8,853,475 |
Kalnes |
October 7, 2014 |
Process for producing a renewable hydrocarbon fuel
Abstract
A process for producing a renewable hydrocarbon fuel. The
process can include providing a feed including a lignocellulosic
material to a pyrolysis zone to produce a stream including a
pyrolysis oil, providing the pyrolysis oil stream to a refining
zone producing a refined stream, providing at least a portion of
the refined stream to a reforming zone producing a stream including
hydrogen, providing at least a portion of the hydrogen stream to
the refining zone; and recovering the renewable hydrocarbon fuel
from the refined stream.
Inventors: |
Kalnes; Tom N. (LaGrange,
IL) |
Applicant: |
Name |
City |
State |
Country |
Type |
Kalnes; Tom N. |
LaGrange |
IL |
US |
|
|
Assignee: |
UOP LLC (Des Plaines,
IL)
|
Family
ID: |
46235232 |
Appl.
No.: |
12/969,335 |
Filed: |
December 15, 2010 |
Prior Publication Data
|
|
|
|
Document
Identifier |
Publication Date |
|
US 20120157729 A1 |
Jun 21, 2012 |
|
Current U.S.
Class: |
585/240; 585/242;
201/28; 201/21; 44/606; 201/29; 44/605 |
Current CPC
Class: |
C10G
1/002 (20130101); C10G 3/42 (20130101); C10G
1/02 (20130101); C10G 3/50 (20130101); C10G
3/44 (20130101); C10G 2400/26 (20130101); C10G
3/49 (20130101); Y02E 50/14 (20130101); Y02E
50/10 (20130101); C10G 3/47 (20130101); Y02P
30/00 (20151101); C10G 3/46 (20130101); Y02P
30/20 (20151101); C10G 2300/4043 (20130101); Y02P
30/10 (20151101); Y02P 20/132 (20151101); Y02P
20/129 (20151101); C10G 2300/207 (20130101); C10G
2300/1014 (20130101) |
Current International
Class: |
C07C
1/00 (20060101) |
Field of
Search: |
;585/240,242 ;44/605,606
;201/21,28,29 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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165839 |
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May 1985 |
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EP |
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2009059936 |
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May 2009 |
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WO |
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2009129622 |
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Oct 2009 |
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WO |
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2009152873 |
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Dec 2009 |
|
WO |
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2010033789 |
|
Mar 2010 |
|
WO |
|
Other References
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Assessment", Envergent Technologies Power Point Presentation for
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2009, p. 24 Pages. cited by applicant .
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Hydrogen by Glycerol Reforming Coupled with Water-Gas-Shift",
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10703, p. 29 pages. cited by applicant .
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35, No. 10, pp. 4962-4969. cited by applicant .
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Process for Production of Gasoline and Diesel Fuel from Biomass",
Conference Proceedings--2009 AIChE Annual Meeting, 09AIChE, Nov.
2009, p. 11 Pages. cited by applicant .
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Abstract Page and pp. 3645-3651. cited by applicant .
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Conversion Science", Conference Brochure for TCBiomass Sep. 16-18,
2009, 2009, p. 8 Pages. cited by applicant.
|
Primary Examiner: Bhat; Nina
Attorney, Agent or Firm: Maas; Maryann
Claims
The invention claimed is:
1. A process for producing a renewable hydrocarbon fuel,
comprising: providing a feed comprising a lignocellulosic material
to a pyrolysis zone to produce a stream comprising a liquid
pyrolysis oil; passing the liquid pyrolysis oil stream to a
refining zone to produce a refined stream; passing at least a
portion of the refined stream to a reforming zone to producing a
stream comprising hydrogen; passing at least a portion of the
hydrogen stream to the refining zone; and recovering a renewable
hydrocarbon fuel from the reforming zone.
2. The process according to claim 1, wherein the lignocellulosic
material comprises at least one of cellulose, hemicellulose, and
lignin.
3. The process according to claim 1, wherein the renewable
hydrocarbon fuel has lifecycle greenhouse gas emissions of no more
than about 40 g CO.sub.2 equivalent/MJ.
4. The process according to claim 1, wherein the reforming zone
comprises a steam reforming zone.
5. The process according to claim 1, further comprising providing
the refined stream to a separation zone to obtain the renewable
hydrocarbon fuel and a fuel gas stream comprising one or more of
CO, CO.sub.2, CH.sub.4, C.sub.2H.sub.6, C.sub.3H.sub.8,
C.sub.4H.sub.10, H.sub.2, and H.sub.2S.
6. The process according to claim 5, wherein the separation zone
comprises one or more flash drums.
7. The process according to claim 5, further comprising passing the
fuel gas stream to a conditioning zone.
8. The process according to claim 7, wherein the conditioning zone
comprises a scrubber.
9. The process according to claim 8, further comprising passing the
scrubbed fuel gas stream to the steam reforming zone.
10. The process according to claim 1, further comprising
pretreating the renewable feed prior to entering the pyrolysis
zone.
11. The process according to claim 10, wherein the pretreating
comprises at least one of sizing, magnetic separation, drying, and
grinding.
12. The process according to claim 1, wherein the pyrolysis zone is
at a temperature of about 300-about 600.degree. C.
13. The process according to claim 1, wherein the refining zone
comprises a reactor containing a catalyst comprising at least one
of cobalt, molybdenum, nickel, tungsten, platinum, palladium,
ruthenium, rhodium, osmium, and iridium.
14. The process according to claim 1, wherein the refining zone is
at a temperature of about 280-about 430.degree. C. and a hydrogen
partial pressure of about 0.7-about 14 MPa.
15. A process for producing a renewable hydrocarbon fuel while
minimizing fossil fuel derived carbon dioxide emissions,
comprising: providing a lignocellulosic material to a pretreating
zone to obtain a pretreated feed; providing the pretreated feed to
a pyrolysis zone to produce a liquid stream comprising a pyrolysis
oil; providing the liquid pyrolysis oil stream to a refining zone
to produce a refined stream; providing the refined stream to a
separation zone to obtain a stream comprising a fuel gas and a
stream comprising one or more hydrocarbons; providing the fuel gas
stream to a conditioning zone to obtain a conditioned stream;
providing the conditioned stream to a reforming zone to obtain a
stream comprising hydrogen; and providing the hydrogen stream to
the refining zone.
16. The process according to claim 15, wherein the reforming zone
comprises an aqueous phase reforming zone.
17. The process according to claim 15, wherein the reforming zone
comprises a steam reforming zone.
18. The process according to claim 15, wherein the separation zone
comprises one or more flash drums.
19. The process according to claim 15, wherein the conditioning
zone comprises a scrubber.
20. A process for producing a renewable hydrocarbon fuel while
minimizing fossil-derived carbon dioxide emissions, comprising:
grinding a lignocellulosic material in a pretreating zone to obtain
a pretreated feed; heating the pretreated feed in a pyrolysis zone
to produce a liquid stream comprising a pyrolysis oil;
hydrotreating the liquid pyrolysis oil in a refining zone to
produce a refined stream; separating the refined stream to obtain a
stream comprising a fuel gas and a stream comprising one or more
hydrocarbons; scrubbing the fuel gas stream; reforming the fuel gas
stream to obtain a stream comprising hydrogen; and, providing the
hydrogen stream to the refining zone.
Description
FIELD OF THE INVENTION
This invention generally relates to a process for producing a
renewable hydrocarbon fuel.
DESCRIPTION OF THE RELATED ART
Generally, concerns over fossil fuel greenhouse gas emissions have
led to an increasing emphasis on renewable energy sources. Wood and
other forms of biomass including agricultural and forestry residues
are examples of some types of biomass feedstocks being considered
for the production of liquid fuels.
Pyrolysis may be used for obtaining liquid fuels from these biomass
feedstocks. Generally, pyrolysis refers to thermal decomposition in
the substantial absence of oxygen or in the presence of
significantly less oxygen than required for complete combustion. In
addition to the desired liquid product, other streams, such as char
ash, and non-condensable gases may be obtained as less desirable
byproducts. However, significantly improved yields of primary,
non-equilibrium liquids and gases, such as valuable chemicals,
chemical intermediates, petrochemicals, and fuels, may be obtained
from carbonaceous feedstocks through fast pyrolysis.
When producing transportation fuels by combination of pyrolysis and
hydrogen refining, a very significant quantity of hydrogen can be
required to produce a fully deoxygenated biofuel meeting ASTM
standards for use as either blend stocks or drop-in replacements
for petroleum gasoline, kerosene, and diesel fuel. If this hydrogen
is supplied by reforming a fossil fuel, the greenhouse gas (may be
abbreviated hereinafter "GHG") footprint for the biofuel can suffer
because the fossil fuel can have a relatively high carbon
footprint. As a consequence, it would be difficult to produce a
biofuel meeting regulatory requirements with a reduced GHG
emission.
SUMMARY OF THE INVENTION
One exemplary embodiment can be a process for producing a renewable
hydrocarbon fuel. The process can include providing a feed
including a lignocellulosic material to a pyrolysis zone to produce
a stream including a pyrolysis oil, providing the pyrolysis oil
stream to a refining zone producing a refined stream, providing at
least a portion of the refined stream to a reforming zone producing
a stream including hydrogen, providing at least a portion of the
hydrogen stream to the refining zone, and recovering the renewable
hydrocarbon fuel from the refined stream.
Another exemplary embodiment may be a process for producing a
renewable hydrocarbon fuel while minimizing fossil fuel derived
carbon dioxide emissions. The process can include providing a
lignocellulosic material to a pretreating zone to obtain a
pretreated feed, providing the pretreated feed to a pyrolysis zone
to produce a stream including a pyrolysis oil, providing the
pyrolysis oil stream to a refining zone producing a refined stream,
providing the refined stream to a separation zone to obtain a
stream including a fuel gas and a stream including one or more
hydrocarbons, providing the fuel gas stream to a conditioning zone
to obtain a conditioned stream, providing the conditioned stream to
a reforming zone to obtain a stream including hydrogen, and
providing the hydrogen stream to the refining zone.
A further exemplary embodiment can be a process for producing a
renewable hydrocarbon fuel while minimizing fossil-derived carbon
dioxide emissions. Generally, the process includes grinding a
lignocellulosic material in a pretreating zone to obtain a
pretreated feed, heating the pretreated feed in a pyrolysis zone to
produce a stream including a pyrolysis oil, hydrotreating the
pyrolysis oil in a refining zone to produce a refined stream,
separating the refined stream to obtain a stream including a fuel
gas and a stream including one or more hydrocarbons, scrubbing the
fuel gas stream, reforming the fuel gas stream to obtain a stream
including hydrogen, and providing the hydrogen stream to the
refining zone.
The embodiments disclosed herein can use a renewable feed,
particularly a lignocellulosic material that can be utilized in a
pyrolysis process that generates multiple liquid streams. At least
one of the liquid streams, such as an aqueous stream rich in water,
can be provided to an aqueous phase reforming zone to reform the
stream as well as generate hydrogen that can be recycled to a
refining zone. In addition, another stream can be provided to a
steam reforming zone for reforming as well as generating hydrogen
that can be recycled to the refining zone. As a result, the life
cycle GHG emissions from refining can be minimized allowing the
production of a biofuel that can meet either local and/or federal
regulatory requirements.
DEFINITIONS
As used herein, the term "stream" can include various hydrocarbon
molecules, such as straight-chain, branched, or cyclic alkanes,
alkenes, alkadienes, and alkynes, and other substances, such as
gases, e.g., hydrogen, carbon oxides, or inorganic impurities, such
as alkali metals, and sulfur and nitrogen compounds. The stream can
also include aromatic and non-aromatic hydrocarbons. Moreover, the
hydrocarbon molecules may be abbreviated C1, C2, C3 . . . Cn where
"n" represents the number of carbon atoms in the one or more
hydrocarbon molecules. Furthermore, a superscript "+" or "-" may be
used with an abbreviated one or more hydrocarbons notation, e.g.,
C3.sup.+ or C3.sup.-, which is inclusive of the abbreviated one or
more hydrocarbons. As an example, the abbreviation "C3.sup.+" means
one or more hydrocarbon molecules of three carbon atoms and/or
more.
As used herein, the term "zone" can refer to an area including one
or more equipment items and/or one or more sub-zones. Equipment
items can include one or more reactors or reactor vessels, heaters,
exchangers, pipes, pumps, compressors, and controllers.
Additionally, an equipment item, such as a reactor, dryer, or
vessel, can further include one or more zones or sub-zones.
As used herein, the term "rich" can mean an amount of at least
generally about 50%, and preferably about 70%, by mole, of a
compound or class of compounds in a stream.
As used herein, the term "substantially" can mean an amount of at
least generally about 80%, preferably about 90%, and optimally
about 99%, by mole, of a compound or class of compounds in a
stream.
As depicted, process flow lines in the figures can be referred to
interchangeably as, e.g., lines, pipes, feeds, products, effluents,
portions, parts, or streams.
As used herein, the term "pyrolysis oil," may refer to an oil
obtained directly from pyrolysis or having undergone treatment such
as filtration to remove solids and/or ion exchange to remove
soluble metals, prior to hydroprocessing.
As used herein, the term "vapor" can mean a gas or a dispersion
that may include or consist of one or more hydrocarbons and/or
water.
As used herein, the term "overhead stream" can mean a stream
withdrawn at or near a top of a column, typically a flash drum or
distillation column.
As used herein, the term "bottom stream" can mean a stream
withdrawn at or near a bottom of a column, typically a flash drum
or distillation column.
As used herein, the terms "alkane" and "paraffin" may be used
interchangeably.
As used herein, the terms "alkene" and "olefin" may be used
interchangeably, and may include one or more olefins and
diolefins.
As used herein, the term "renewable hydrocarbon fuel" may be any
fuel at least partially derived from sources other than a fossil
fuel. A renewable hydrocarbon fuel can include renewable naphtha
and renewable diesel, and having a distillation range as defined
by, e.g., ASTM Test Method D86 or D2887.
As used herein, the term "fossil fuel" can mean any fuel derived
from animal or vegetable sources in past geologic ages buried in
the earth. Exemplary fossil fuels may include petroleum, natural
gas, coal, and lignite.
As used herein, a lifecycle greenhouse gas emission value can be
based on carbon dioxide equivalents, as measured according to
guidelines set forth by the Intergovernmental Panel on Climate
Change (IPCC) and the U.S. Federal Government. Lifecycle assessment
values of emissions in terms of carbon dioxide equivalents, from
raw material cultivation (in the case of plant materials) or raw
material extraction (in the case of fossil fuels) through fuel
combustion, can be calculated using SimaPro 7.1 software and IPCC
GWP 100a methodologies and provide in units of grams of carbon
dioxide equivalent per mega joule (herein may be abbreviated "g
CO.sub.2 equivalent/MJ").
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic depiction of an exemplary biofuel production
facility.
DETAILED DESCRIPTION
Referring to FIG. 1, a biofuel production facility 10 can include a
pretreating zone 100, a pyrolysis zone 140, a refining zone 180, a
separation zone 200, a conditioning zone 220, a reforming zone 240,
a fractionation zone 260, and another reforming zone 280.
Generally, the biofuel production facility 10 can receive a feed 50
including one or more carbonaceous feedstocks that are classified
as renewable. Typically, the feed 50 can be any biomass material or
mixture of biomass materials having lignocellulosic material,
including a hardwood, a softwood, a hardwood or softwood bark, or
logging residues. The feed 50 may also include energy crops,
agricultural residues, or other types of plant wastes or
plant-derived wastes. Specific exemplary plant materials may
include corn fiber, corn stover, and sugar cane bagasse, in
addition to "on-purpose" energy crops such as switchgrass,
miscanthus, and algae. Generally, short rotation forestry products,
as energy crops, include alder, ash, southern beech, birch,
eucalyptus, poplar, willow, paper mulberry, Australian blackwood,
sycamore, and varieties of paulownia elongate. Other examples of
suitable biomass can include organic waste materials, such as waste
paper and construction, demolition, and municipal wastes. In
general, the feed 50 may include any biomass including
lignocellulosic material. Because the lignocellulosic biomass may
be composed of the same building blocks, namely cellulose,
hemicellulose, and lignin, pyrolysis conditions can be relatively
similar for processing varying feeds.
The feed 50 can be provided to a pretreating zone 100. The
pretreating zone 100 can utilize any suitable process for reducing
the feed 50 to a suitable material for being processed by the
pyrolysis zone 140. The pretreating process can include at least
one of sizing, magnetic separation, drying, and grinding. Such
pretreating processes are disclosed in, e.g., US 2010/0140136
A1.
Afterwards, a pretreated feed 120 can be provided to the pyrolysis
zone 140. The pyrolysis zone 140 can operate under any suitable
conditions, such as a temperature of about 300-about 600.degree. C.
and a residence time of about 0.1-about 5 seconds. Exemplary
pyrolysis zones and operating conditions are disclosed in, e.g.,
U.S. Pat. No. 5,792,340 and US 2009/0239279 A1. The pyrolysis zone
140 can include any suitable pyrolysis reactor, such as a
fluidized-bed reactor, a transport reactor, a cyclonic ablative
reactor, or a vacuum pyrolysis reactor.
The pyrolysis zone 140 can provide a solid byproduct stream 144, an
aqueous byproduct stream 148 rich in water, a gas byproduct stream
152, and a pyrolysis oil stream 160. The aqueous byproduct stream
148 can optionally be provided to another reforming zone 280, which
can be an aqueous phase reforming zone, such as disclosed in, e.g.,
U.S. Pat. No. 6,964,758 B2. Typically, the reaction is conducted in
a condensed liquid phase over a metal catalyst impregnated on a
water-compatible support. The reaction can be conducted at any
suitable temperature and pressure.
The reforming zone 280 can process the aqueous byproduct stream 148
to produce one or more hydrocarbons as a stream 282 as well as a
hydrogen stream 284. Optionally, the hydrogen stream 284 can be
recycled to the refining zone 180, as hereinafter described.
Usually, the hydrogen generated from the aqueous byproduct stream
148 can supplement or even provide the quantities of hydrogen
required by the refining zone 180.
The pyrolysis zone 140 can produce the pyrolysis oil stream 160.
Typically, the pyrolysis oil stream 160 includes a mixture of
water, organic compounds having lower water solubility, and other
oxygenated hydrocarbons having higher water solubility, e.g.,
aldehydes, ketones, alcohols, and phenolics.
Fast pyrolysis can involve rapid heat transfer to the pretreated
feed 120, which can be maintained at a relatively high temperature
for a very short time. The temperature of the primary pyrolysis
products may then be rapidly reduced before achieving chemical
equilibrium. The fast cooling can prevent the valuable reaction
intermediates, formed by depolymerization and fragmentation of the
biomass building blocks, namely cellulose, hemicellulose, and
lignin, from degrading to lesser value final products.
The pyrolysis oil stream 160 can be acidic with a pH of less than
about 4.0. Generally, the water molecules are split during
pyrolysis and held separately in other compounds within the complex
pyrolysis liquid. Thus, the "water" in pyrolysis oil may not
separate from the organic fraction of the pyrolysis oil as a phase
as in standard petroleum-derived fuels. Generally, the pyrolysis
oil stream 160 contains about 30-about 35%, by weight, of oxygen in
the form of organic oxygenates such as hydroxyaldehydes,
hydroxyketones, sugars, carboxylic acids, and phenolic oligomers as
well as dissolved water. For this reason, although a pourable and
transportable liquid fuel, usually the pyrolysis oil, has only
about 55-about 60% of the energy content of crude oil-based fuel
oils. Generally, representative values of the energy content are in
the range from about 19.0-about 25.0 MJ/liter.
Properties of a pyrolysis oil can include a heating value of about
15-about 21 MJ/kg, a pour point of about -12-about -33.degree. C.,
no cloud point observed until about -21.degree. C., a carbon
residue of about 17-about 23%, by weight, based on the weight of
the pyrolysis oil, and a flash point of about 40-about 100.degree.
C. As such, the pyrolysis oil may not auto-ignite in a diesel
engine, and the cetane number can be significantly less than ASTM
requirements for use in transportation vehicle service, e.g., less
than about 25.
While the exact composition of the pyrolysis oil usually depends on
the feed 50 and processing conditions, a typical composition is as
follows:
TABLE-US-00001 TABLE 1 Amount Component (%, By Weight) Water about
20-about 28 Suspended solids and about 22-about 36 pyrolitic lignin
Hydroxyacetaldehyde about 8-about 12 Levoglucosan about 3-about 8
Acetic acid about 4-about 8 Acetol about 3-about 6 Cellubiosan
about 1-about 2 Glyoxal about 1-about 2 Formaldehyde about 3-about
4 Formic Acid about 3-about 6
The pyrolysis oil stream 160 can be combined with a portion of a
recycle stream 270 as hereinafter described, to form a combined
stream 164 to the refining zone 180. Generally, the refining zone
180 hydrogenates and deoxygenates the pyrolysis oil stream 160.
Often, the raw pyrolysis product is corrosive and exhibits chemical
instability due to the presence of highly unsaturated compounds
such as olefins and alkenylaromatics. Hydroprocessing of this
pyrolysis oil stream 160 in the refining zone 180 can reduce its
oxygen content and increase its stability, thereby rendering a
refined product more suitable for blending in fuels, such as
gasoline or diesel. Refining involves contacting the pyrolysis oil
with hydrogen and in the presence of a suitable catalyst, generally
under conditions sufficient to convert a large proportion of the
organic oxygen in the raw pyrolysis oil to carbon monoxide, carbon
dioxide, and water that are easily removed.
The catalyst may be present in the form of a fixed bed of
particles, including a catalytically active metal disposed on a
support, with suitable metals and supports being described below.
Otherwise, the catalyst either supported or otherwise unsupported,
in the form of fine particles of a compound containing the
catalytically active metal, may be used in an ebullated bed or a
back-mixed multi-phase bed, such as in the case of a slurry
reactor. Homogeneous systems operating with catalysts soluble in
the reactants and products may also be used. Catalytic refining
conditions can vary depending on the quality of the refined
pyrolysis oil desired, with higher severity operations
directionally resulting in greater conversion of organic oxygenates
and other undesirable compounds, e.g., reactive olefins and
diolefins by hydrogenation.
Typically, refining conditions include an average catalyst bed
temperature from about 40-about 540.degree. C., preferably about
280-about 430.degree. C., and a hydrogen partial pressure from
about 0.7-about 21 MPa or about 2.8-about 21 MPa, preferably about
0.7-about 14 MPa or about 5-about 14 MPa. A typical range of liquid
hourly space velocity (herein may be abbreviated "LHSV") for
hydroprocessing may be about 0.1-about 10 hr.sup.-1, preferably
about 0.3-about 3 hr.sup.-1. Generally, a sufficient quantity of
hydrogen is provided to convert organic oxygenates to hydrocarbons
and water. The refining zone 180 can receive hydrogen from the
reforming zone 240 and the another reforming zone 280 via,
respectively, the stream 252 and the stream 284.
Suitable refining catalysts include those having at least one Group
VIII (IUPAC 8-10) metal, such as iron, cobalt, and nickel and at
least one Group VI (IUPAC 6) metal, such as molybdenum and
tungsten, on a high surface area support material such as a
refractory inorganic oxide, e.g., silica, alumina, titania, and/or
zirconia support or a carbon support. Preferably, the catalyst
includes at least one of cobalt, molybdenum, nickel, tungsten,
platinum, palladium, ruthenium, rhodium, osmium, and iridium.
Typically, the Group VIII metal is present in the catalyst in an
amount ranging from about 2-about 20%, by weight, and preferably
about 4-about 12%, by weight, based on the volatile-free catalyst
weight. Usually, the Group VI metal is present in an amount ranging
from about 1-about 25%, by weight, and preferably about 2-about
25%, by weight, also based on the volatile-free catalyst weight. A
volatile-free catalyst sample may be obtained by subjecting the
catalyst to drying at about 200-about 350.degree. C. under an inert
gas purge or vacuum for a period of time, e.g., about 2 hours, to
drive water and other volatile components from the catalyst.
Other suitable refining catalysts include zeolitic catalysts, as
well as noble metal catalysts where the noble metal is selected
from palladium and platinum. More than one type of refining
catalyst may be utilized in the same or different reaction vessel.
Other suitable refining zones and operating conditions for
hydrogenating, hydrotreating, and/or isomerizing are disclosed in,
e.g., US 2009/0287029 A1.
After refining, the resulting oil has an oxygen content that is
generally reduced from about 90-about 99.9%, relative to the oxygen
content of the pyrolysis oil. Typically, the heating value, on a
mass basis, of the refined pyrolysis oil is simultaneously
increased, usually by a factor of about 1.5-about 3, compared to
that of unrefined pyrolysis oil.
The refining zone 180 can provide a refined stream 184 to a
separation zone 200. Typically, any separation device can be
utilized, such as one or more flash drums. In one exemplary
embodiment, a series of high, medium, and optionally low pressure
flash drums can be utilized to remove gaseous components that can
be combined as a fuel gas stream 210 and a stream 214 including one
or more hydrocarbons. Therefore, the fuel gas stream 210 can
include one or more of CO, CO.sub.2, CH.sub.4, C.sub.2H.sub.6,
C.sub.3H.sub.8, C.sub.4H.sub.10, H.sub.2, and H.sub.2S. Usually, a
high pressure flash drum can operate at about 5-about 21 MPa, a
medium pressure flash drum can operate at about 3-about 14 MPa, and
a low pressure flash drum can operate at about 1-about 7 MPa.
The fuel gas stream 210 can be provided to a conditioning zone 220.
Typically, the conditioning zone 220 can include one or more
scrubbers, such as an amine scrubber. The fuel gas stream 210 can
include one or more gases, such as one or more C1-C4 hydrocarbons,
typically alkanes, carbon monoxide, carbon dioxide, and hydrogen.
The conditioning zone can include one or more scrubbers to remove
hydrogen sulfide, carbon dioxide, and optionally ammonia. Usually,
the conditioning zone 220 can include a water wash column. An
exemplary conditioning zone is disclosed in, e.g., US 2009/0287029
A1. After scrubbing, the conditioning zone 220 may optionally also
contain one or more vessels for conducting a water shift reaction
to convert the carbon monoxide and water to carbon dioxide and
hydrogen.
The conditioned stream 230, optionally combined with a make-up fuel
gas stream 234, can form a combined stream 238 and be provided to a
reforming zone 240. Typically, the reforming zone 240 is a steam
reforming zone, as disclosed in, e.g., US 2009/0287029 A1, which
may provide hydrogen to the refining zone 180. Usually, a
hydrocarbon and steam mixture is catalytically reacted at high
temperature to form hydrogen and the carbon oxides, such as carbon
monoxide and carbon dioxide. Because the reforming reaction is
strongly endothermic, heat is typically supplied by a furnace to
the reactant mixture.
One exemplary steam reforming process is autothermal reforming,
also called catalytic partial oxidation, which may supply heat by
the partial internal combustion of a feed with oxygen or air.
Generally, exit temperatures may range from about 500-about
950.degree. C. and pressures may be up to about 6 MPa.
The steam reforming product may be recycled to any of the reaction
zones to provide at least hydrogen to the reaction zone.
Optionally, the hydrogen may be separated from the carbon oxides
generated in the steam reforming reaction, and the separated
hydrogen may be recycled to the refining zone 180.
Generally, the reforming zone 240 can not only reform the fuel gas
stream to provide components that may optionally be used in fuel,
but can also provide power and steam as indicated by the line 248.
In addition, a hydrogen stream 252 can be obtained that may
optionally pass through a compressor and be provided back to the
refining zone 180. Optionally, the hydrogen stream 252 can be
purified in a pressure swing absorber prior to being provided to
the refining zone 180. As such, the reforming zone 240 can not only
provide hydrogen, but also power to the biofuel production facility
10. As such, this recycling of components can minimize the
greenhouse gas emissions of any subsequent renewable hydrocarbon
fuel produced.
The one or more hydrocarbons in the stream 214 from the separation
zone 200 can be provided to a fractionation zone 260. The
fractionation zone 260 can produce a fuel gas stream 262; a first
renewable hydrocarbon fuel stream 264, typically a renewable
naphtha or gasoline; a second renewable hydrocarbon fuel stream
266, typically a renewable diesel; and a bottom stream 268.
Typically, the naphtha or gasoline has an initial boiling point
temperature characteristic of C5 hydrocarbons, for example from
about 30-about 40.degree. C. and a distillation end point
temperature generally of about 130-about 220.degree. C., and
typically about 130-about 160.degree. C. The boiling point range of
naphtha or gasoline may be about 20-about 180.degree. C.,
preferably about 50-about 150.degree. C. The renewable diesel can
have boiling point characteristics similar to petroleum fuel and
may have a range of about 120-about 380.degree. C., preferably
about 150-about 350.degree. C. These boiling point temperatures,
which are also characteristic of petroleum derived gasoline and
diesel, may be measured according to ASTM D86. In one exemplary
embodiment, the fuel gas stream 262 can include one or more
C4.sup.- hydrocarbons. Optionally, at least a portion of these
biomass-derived C4.sup.- hydrocarbons can be provided to the
reforming zone 240 to generate at least a portion of the hydrogen
for the refining zone 180.
The bottom stream 268 can include one or more heavier hydrocarbons,
such as one or more C9.sup.+ hydrocarbons, which can be recycled to
at least one of the refining zone 180 as a portion 270 or to the
pyrolysis zone 140 as another portion 274. The recycle to the
pyrolysis zone 140 can be provided to the reactor outlet as a more
thermally stable quench oil for cooling the hot pyrolysis vapor
leaving the pyrolysis reactor. Quenching the hot vapor can quickly
stop the thermal reactions and prevent polymerization and the
associated formation of high molecular weight oxygenated
hydrocarbons. When the bottom stream 268 is recycled to the
refining zone 180, the temperature rise can be favorably buffered.
In addition, the concentration of reactive species entering the
refining zone 180 is diluted with a more thermally stable and
hydrogen rich bottom stream 268 so as to minimize undesirable side
reactions that can lead to high coke formations. In addition,
removing the bottom stream 268 from the fractionation zone 260 can
not only provide the recycle streams 270 and 274, but a portion of
this heavier hydrocarbon can be taken as a product stream 278.
The embodiments disclosed herein can provide a process utilizing a
renewable hydrogen stream to reduce carbon emissions. In one
estimate, utilizing such a renewable feed in a pyrolysis process
can reduce lifecycle greenhouse gas emissions of about 80% or more
for producing a renewable hydrocarbon or transportation fuel,
usually renewable gasoline, as compared to a petroleum derived
transportation fuel.
Without further elaboration, it is believed that one skilled in the
art can, using the preceding description, utilize the present
invention to its fullest extent. The preceding preferred specific
embodiments are, therefore, to be construed as merely illustrative,
and not limitative of the remainder of the disclosure in any way
whatsoever.
In the foregoing, all temperatures are set forth in degrees Celsius
and, all parts and percentages are by weight, unless otherwise
indicated.
From the foregoing description, one skilled in the art can easily
ascertain the essential characteristics of this invention and,
without departing from the spirit and scope thereof, can make
various changes and modifications of the invention to adapt it to
various usages and conditions.
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